The influence of bottom topography on the decay of modeled Agulhas rings

The influence of a large meridional submarine ridge on the decay of Agulhas rings is investigated with a 1 and 2-layer setup of the isopycnic primitive-equation ocean model MICOM. In the single-layer case we show that the SSH decay of the ring is primarily governed by bottom friction and secondly by the radiation of Rossby waves. When a topographic ridge is present, the effect of the ridge on SSH decay and loss of tracer from the ring is negligible. However, the barotropic ring cannot pass the ridge due to energy and vorticity constraints. In the case of a two-layer ring the initial SSH decay is governed by a mixed barotropic–baroclinic instability of the ring. Again, radiation of barotropic Rossby waves is present. When the ring passes the topographic ridge, it shows a small but significant stagnation of SSH decay, agreeing with satellite altimetry observations. This is found to be due to a reduction of the growth rate of the m = 2 instability, to conversions of kinetic energy to the upper layer, and to a decrease in Rossby-wave radiation. The energy transfer is related to the fact that coherent structures in the lower layer cannot pass the steep ridge due to energy constraints. Furthermore, the loss of tracer from the ring through filamentation is less than for a ring moving over a flat bottom, related to a decrease in propagation speed of the ring. We conclude that ridges like the Walvis Ridge tend to stabilize a multi-layer ring and reduce its decay.

A reconstructed Siberian High index since A. D. 1599 from Eurasian and North American tree rings

The long-term variability of the Siberian High, the dominant Northern Hemisphere anticyclone during winter, is largely unknown. To investigate how this feature varied prior to the instrumental record, we present a reconstruction of a Dec-Feb Siberian High (SH) index based on Eurasian and North American tree rings. Spanning 1599-1980, it provides information on SH variability over the past four centuries. A decline in the instrumental SH index since the late 1970s, related to Eurasian warming, is the most striking feature over the past four hundred years. It is associated with a highly significant (p < 0.0001) step change in 1989. Significant similar to 3-4 yr spectral peaks in the reconstruction fall within the range of variability of the East Asian winter monsoon (which has also declined recently) and lend further support to proposed relationships between these largescale features of the climate system.

Spectral functions of half-filled one-dimensional Hubbard rings with varying boundary conditions

We study the effect of varying the boundary condition on: the spectral function of a finite one-dimensional Hubbard chain, which we compute using direct (Lanczos) diagonalization of the Hamiltonian. By direct comparison with the two-body response functions and with the exact solution of the Bethe ansatz equations, we can identify both spinon and holon features in the spectra. At half-filling the spectra have the well-known structure of a low-energy holon band and its shadow-which spans the whole Brillouin zone-and a spinon band present for momenta less than the Fermi momentum. Features related to the twisted boundary condition are cusps in the spinon band. We show that the spectral building principle, adapted to account for both the finite system size and the twisted boundary condition, describes the spectra well in terms of single spinon and holon excitations. We argue that these finite-size effects are a signature of spin-charge separation and that their study should help establish the existence and nature of spin-charge separation in finite-size systems.

On the fast decay of Agulhas rings

The Indian Ocean water that ends up in the Atlantic Ocean detaches from the Agulhas Current retroflection predominantly in the form of Agulhas rings and cyclones. Using numerical Lagrangian float trajectories in a high-resolution numerical ocean model, the fate of coherent structures near the Agulhas Current retroflection is investigated. It is shown that within the Agulhas Current, upstream of the retroflection, the spatial distributions of floats ending in the Atlantic Ocean and floats ending in the Indian Ocean are to a large extent similar. This indicates that Agulhas leakage occurs mostly through the detachment of Agulhas rings. After the floats detach from the Agulhas Current, the ambient water quickly looses its relative vorticity. The Agulhas rings thus seem to decay and loose much of their water in the Cape Basin. A cluster analysis reveals that most water in the Agulhas Current is within clusters of 180 km in diameter. Halfway in the Cape Basin there is an increase in the number of larger clusters with low relative vorticity, which carry the bulk of the Agulhas leakage transport through the Cape Basin. This upward cascade with respect to the length scales of the leakage, in combination with a power law decay of the magnitude of relative vorticity, might be an indication that the decay of Agulhas rings is somewhat comparable to the decay of two-dimensional turbulence.

Design of supramolecular beta-sheet forming beta-turns containing aromatic rings and non-coded alpha-aminoisobutyric acid and the formation of flat fibrillar structures through self-assembly

Single crystal X-ray diffraction studies show that the three designed tripeptides Boc-Leu-Aib-m-NA-NO2 (I), Boc-Phe-Aib-m-NA-NO2 (II) and Boc-Pro-Aib-m-ABA-OMe (III) (Aib, -aminoisobutyric acid; m-NA, m-nitroaniline; m-ABA, m-aminobenzoic acid; Boc, t-butyloxycarbonyl) containing aromatic rings in the backbones adopt -turn structures that are self-assembled through intermolecular hydrogen bonds and van der Waals interactions to create layers of -sheets. Solvent-dependent NMR titration and CD studies show that the -turn structures of the peptides also exist in the solution phase. The field emission scanning electron microscopic and transmission electron microscopic images of the peptides in the solid state reveal fibrillar structures of flat morphology that are formed through -sheet mediated self-assembly of the preorganised -turn building blocks.

Synthesis of fused cyclic systems containing medium-sized rings through tandem ROM-RCM of norbornene derivatives embedded in a carbohydrate template

A general approach for the synthesis of fused cyclic systems containing medium-sized rings (7-9) has been developed. The key steps involve a diastereoface-selective Diels-Alder reaction of the dienophiles 4a-d attached to a furanosugar with cyclopentadiene and ring opening (ROM)-ring closing metathesis (RCM) of the resulting norbornene derivatives 10a-d and 11a-d. Diels-Alder reaction of the dienophiles 4a-d with cyclopentadiene in the absence of a catalyst produced 10a-d as the major product arising through addition of the diene to the unhindered Si-face. The most interesting and new aspect of the Diels-Alder reaction of these dienophiles is the accessibility of the Re-face that was blocked by the alkenyl chains under Lewis acid catalysis producing the diastereoisomers 11a-d exclusively. The reversal of facial selectivity from an uncatalyzed reaction to a catalyzed one is unprecedented. The observed stereochemical dichotomy is attributed to rotation of the enone moiety along the or bond linking the sugar moiety during formation of the chelate 13. This makes the Re-face of the enone moiety in 4a-d unhindered. Diels-Alder reaction of the carbocyclic analogue 15 under Lewis acid catalysis produced a 1: 1 mixture of the adducts 16 and 17 confirming the participation of sugar ring oxygen in chelate formation. Finally ROM-RCM of 10a-d and 11a-d with Grubbs' catalyst afforded the cis-syn-cis and cis-anti-cis bicyclo-annulated sugars 21a-d and 23a-d, respectively, containing 7-9 membered rings.

Mononuclear and binuclear ruthenium(II) complexes with 4-(phenyl) thiosemicarbazone of benzaldehyde: a discussion on the relative stabilities of the four-membered and five-membered chelate rings formed by the ligand

Three new ruthenium complexes of the formulae cis-[Ru(PPh3)(2)(BzTscbz)(2)] (1a), [Ru-2(PPh3)(2)(BzTscbz)(4)] (1b) and [Ru(PPh3)(2)(BzTscHbz)(2)](ClO4)(2) (2) [BzTscHbz = 4-(phenyl) thiosemicarbazone of benzaldehyde] have been synthesized and characterized by various physicochemical methods including X-ray structure determinations for 1a and 1b. The relative stabilities of the four-membered versus five-membered chelate rings formed by the deprotonated ligand BzTscbz are discussed on the basis of the experimental results and some semi-empirical as well as DFT calculations. (c) 2005 Elsevier Ltd. All rights reserved.

Fast northward energy transfer in the Atlantic due to Agulhas rings

The adiabatic transit time of wave energy radiated by an Agulhas ring released in the South Atlantic Ocean to the North Atlantic Ocean is investigated in a two-layer ocean model. Of particular interest is the arrival time of baroclinic energy in the northern part of the Atlantic, because it is related to variations in the meridional overturning circulation. The influence of the Mid-Atlantic Ridge is also studied, because it allows for the conversion from barotropic to baroclinic wave energy and the generation of topographic waves. Barotropic energy from the ring is present in the northern part of the model basin within 10 days. From that time, the barotropic energy keeps rising to attain a maximum 500 days after initiation. This is independent of the presence or absence of a ridge in the model basin. Without a ridge in the model, the travel time of the baroclinic signal is 1300 days. This time is similar to the transit time of the ring from the eastern to the western coast of the model basin. In the presence of the ridge, the baroclinic signal arrives in the northern part of the model basin after approximately 10 days, which is the same time scale as that of the barotropic signal. It is apparent that the ridge can facilitate the energy conversion from barotropic to baroclinic waves and the slow baroclinic adjustment can be bypassed. The meridional overturning circulation, parameterized in two ways as either a purely barotropic or a purely baroclinic phenomenon, also responds after 1300 days. The ring temporarily increases the overturning strength. Th presence of the ridge does not alter the time scales.

An unusual axial–axial combination of alternating cyclic rings in the chair conformations of hexameric water and chlorine-water clusters

An alternating hexameric water (H2O)(6) cluster and a chlorine-water cluster [Cl-2(H2O)(4)](2-) in the chair forms combine axially to each other to form a 1D chain [{Cl-2(H2O)(6)}(2-)](n) in complex [FeL2]Cl center dot(H2O)(3) (L=2-[(2-methylaminoethylimino)-methyl]-phenol)]. The water molecules display extensive H-bonding interactions with monomeric iron-organic units to form a hydrogen-bonded 2D supramolecular assembly.

Tracer Leakage from Modeled Agulhas Rings

In a numerical, isopycnal, ocean model the mixing is investigated with the environment of two idealized Agulhas rings, one that splits, and one that remains coherent. The evolution of a passive tracer , initially contained within the rings, shows that tracer leakage is associated with the for mation of filaments in the early stage of ring evolution. These filaments reach down to the ther mocline. In the deepest layers leakage occurs on a larger scale. Self-advection of the rings is ver y irregular , and it is not possible to compute a Lagrangian boundar y i n order to estimate the transport of leakage from the rings. T o describe the processes that gover n tracer leakage, in a coordinate frame moving with the ring a kinematic separatrix is defined in the streamfunction field for the nondivergent flow . Initially , filaments arise because of the elongation of the ring, which is mainly gover ned by an m 5 2 instability that is collaborating with differential rotation. Because of beta, the symmetr y i s destroyed related to the separatrix associated with a stagnation point in the flow . The filament upstream of the stagnation point grows much faster and is associated with the bulk of tracer leakage. Mixing is enhanced by time dependence of the separatrix. As a result, there are no large differences between the leakage from a coherent ring, where the m 5 2 instability equilibrates, and from a splitting ring, where the m 5 2 instability keeps growing, which confir ms that the amount of leakage is mainly gover ned by the ring’ s initial defor mation combined with unsteady self-advection of the ring and not by the splitting of the ring. The decay of tracer content in the ther mocline shows that in the first months up to 40% of the ring water can be mixed with the environment. In deeper layers the decay of tracer content may reach up to 90%.

Translation, decay and splitting of Agulhas rings in the southeastern Atlantic Ocean

All Agulhas rings that were spawned at the Agulhas retrofiec- tion between 1993 and 1996 (a total of 21 rings) have been monitored using TOPEX/Poseidon satellite altimetry and followed as they moved through the southeastern Atlantic Ocean, decayed, interacted with bottom topography and each other, or dissipated completely. Rings preferentially crossed the Walvis Ridge at its deepest parts. After having crossed this ridge they have lower translational speeds, and their decay rate decreases markedly. Half the decay of long-lived rings takes place in the first 5 months of their lifetimes. In addition to the strong decay of rings in the Cape Basin, about one third of the observed rings do not seem to leave this region at all but totally disintegrate here. The interaction of rings with bottom topography, in particular with the Verna Seamount, is shown frequently to cause splitting of rings. This will enhance mixing of the rings' Indian Ocean water into that of the southern Atlantic. This localized mixing may well provide a considerable source of warm and salty Indian Ocean water into the Atlantic overturning circulation.